CN105779984A - Chromate-free passivation agent for aluminum alloy - Google Patents
Chromate-free passivation agent for aluminum alloy Download PDFInfo
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- CN105779984A CN105779984A CN201610248170.0A CN201610248170A CN105779984A CN 105779984 A CN105779984 A CN 105779984A CN 201610248170 A CN201610248170 A CN 201610248170A CN 105779984 A CN105779984 A CN 105779984A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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Abstract
The invention discloses a chromate-free passivation agent for an aluminum alloy. Per liter of chromate-free passivation agent is composed of, by mass, 10 mg to 300 mg of amino silane or/and epoxy silane, 1 mg-100 mg of dispersible nano particles, 10 mg-500 mg of a zirconium compound or/and a titanium compound, 1 mg-150 mg of metal ions, 10 mg-150 mg of fluoride, 1 mg-20 mg of a complexing agent, 75 mg-100 mg of organic phosphoric acid and the balance water; and the organic phosphoric acid is at least two of HEDP, HPMA, EDTMP, DTPMP, ATMP and PBTCA. According to the passivation agent, multiple kinds of organic phosphoric acid, multiple kinds of metal ions and multiple kinds of nano particles are chelated to the different degrees; on one aspect, the thickness and the compactness of a passivation film layer can be strengthened; and meanwhile, the passivation film layer (inorganic film layer) formed after chelation can show a color to a certain degree on the surface of the aluminum alloy.
Description
Technical field
The present invention relates to a kind of passivator without chromium, manganese element, particularly relate to a kind of suitable in the chrome-free tanning agent before aluminium alloy application.
Background technology
The Al alloy parts of the type such as aluminium section bar or aluminium wheels typically requires before application and carries out surface treatment to strengthen the adhesion property between metal and coating, at present, and the aluminum alloy surface treatment technology many employings Cr VI passivation process before application.But, this processing method is containing Cr VI heavy metal ion, and toxicity is big, and environmental pollution is serious, and the harmful substances such as such as Cr VI are proposed clear and definite restriction requirement by the enforcement of European Union RoHS environmental protection instruction.Therefore, it is always up a focus in the research of aluminum alloy surface process Trend of Chrome-free technology both at home and abroad in the last few years.
Currently as the chromium-free deactivation technology that can substitute tradition hexavalent chromium-treatments mode, including zirconium titanium system, molybdate system, rare-earth salts system and organosilane systems etc..These known chromium-free treatment technology all can effectively solve the problem that the problems such as the environmental pollution that Cr VI passivating technique brings.But there is a certain distance in the passivation effect of these chromium-free deactivation technology and Cr VI technology.Additionally, traditional Cr VI passivator can manifest certain color at the rete that aluminum alloy surface is formed, operator are facilitated to judge the process of reaction, and current chromium-free deactivation technology is all colourless at the rete that aluminum alloy surface is formed, to site operation personnel, this judges whether that forming rete causes certain puzzlement.Therefore a kind of both had good inactivating performance, and the exploitation of the chrome-free tanning agent that the rete concurrently formed can demonstrate color in aluminum alloy surface again is necessary.
Summary of the invention
Goal of the invention: the technical problem to be solved is to provide a kind of chrome-free tanning agent suitable in aluminium alloy, this passivator can strengthen thickness and the consistency of aluminum alloy surface passivation film on the one hand, it addition, the passivation film of formation can also be made to demonstrate color in aluminum alloy surface.
Summary of the invention: for solving above-mentioned technical problem, the technical solution adopted in the present invention is:
A kind of chrome-free tanning agent suitable in aluminium alloy, for every L chrome-free tanning agent, be made up of the component of following quality: the amino silane of 10～300mg or/and epoxy silane, the dispersibility nanoparticle of 1～100mg, 10～500mg zirconium compounds or/and titanium compound, the metal ion of 1～150mg, the fluoride of 10～150mg, 1～20mg chelating agent, the organic phosphoric acid of 75～100mg and surplus are water；Wherein, described organic phosphoric acid is at least two in HEDP, HPMA, EDTMP, DTPMP, ATMP and PBTCA.
nullIt is preferred that，Described amino silane is γ-aminopropyltrimethoxysilane、Gamma-aminopropyl-triethoxy-silane、γ-aminopropyltriethoxy dimethoxysilane、γ-aminopropyltriethoxy diethoxy silane、N-methyl-γ-aminopropyltrimethoxysilane、N-(normal-butyl)-γ-aminopropyltrimethoxysilane、N-(normal-butyl)-gamma-aminopropyl-triethoxy-silane、N，N-diethyl-γ-aminopropyltrimethoxysilane、3-cyclohexyl-aminopropyltriethoxy dimethoxysilane、Anilinomethyl trimethoxy silane、Anilinomethyl triethoxysilane、N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane、N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane、N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane、N-(β-aminoethyl)-γ-aminopropyltriethoxy diethoxy silane、Aminoethyl ammonia isobutyl methyl dimethoxysilane、3-(2-ethoxy aminoethyl)-aminopropyltriethoxy dimethoxysilane、Diethylenetriamine base hydroxypropyl methyl dimethoxysilane、At least one in double; two [3-(trimethoxy-silylpropyl)] amine or double; two [3-(triethoxysilylpropyltetrasulfide)] amine.The low silane rete then formed in metal surface of amino silane content in passivator will not be close, and content is high unstable situation then easily occurs.
It is preferred that, described epoxy silane is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane, γ-glycydoxy triethoxysilane, γ-glycydoxy methyldiethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, at least one in 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane.The low silane rete then formed in metal surface of epoxy silane content in passivator will not be close, and content is high unstable situation then easily occurs.
It is preferred that, described dispersibility nanoparticle is SiO2Nanoparticle, ZrO2Nanoparticle, HfO2Nanoparticle, LaO2Nanoparticle, CeO2Nanoparticle, TiO2Particle, Al2O3Nanoparticle, MnO2Nanoparticle, MoO3Nanoparticle, CuO nanoparticle, B2O3Nanoparticle or Co2O3Any two or three nanoparticle in nanoparticle.Dispersibility nanoparticle content in passivator is low, can not play the effect of effective film forming, and content is high unstable situation then easily occurs.
It is preferred that, described zirconium compounds is at least one in fluorine zirconic acid, zirconium oxychloride, zirconium carbonate, zirconium nitrate or zirconyl nitrate.Zirconium compounds content in passivator is low, can not play the effect of effective film forming, and content height then film quality declines on the contrary.
It is preferred that, described titanium compound is fluotitanic acid or titanyl sulfate.Titanium compound content in passivator is low, can not play the effect of effective film forming, and content height then film quality declines on the contrary.
It is preferred that, described metal ion is the metal ion in rare earth element or at least two in Fe, Mg, Co, Cu, Zn or Mo.Metal ion content in passivator is low, can not play the effect effectively facilitating film forming, and content height then film quality can decline to some extent.
It is preferred that, described fluoride is sodium fluoride or potassium fluoride, and the existence of fluoride and proper content can effectively control the response speed of aluminum alloy surface, and deposition and colour developing degree to rete play beneficial effect.
It is preferred that, described chelating agent is at least one in sodium citrate, sodium tartrate, oxalic acid, malic acid, succinic acid or malonic acid, and steady operation liquid and control film deposition speed are had a positive effect by the existence of chelating agent and proper content.
It is preferred that, in every L chrome-free tanning agent, possibly together with a certain amount of surfactant, described surfactant is the one in cationic surface active agent, anionic surfactant, amphoteric surfactant or nonionic surfactant.
Beneficial effect: multiple organic phosphoric acid is added containing in the system being made up of polytype metal ion, nanoparticle and silane coupler by passivator of the present invention, chelating in various degree can be there is in organic phosphoric acid with metal ion, nanoparticle, thickness and the consistency of passivation film, the further antiseptic property improving passivation film and the physical bond ability with post-coatings can be strengthened on the one hand；The passivation film (inorganic film) simultaneously formed after chelating and the combined effect of other compositionss can show a degree of color in aluminum alloy surface, and therefore site operation personnel can quickly judge whether aluminum alloy surface defines passivation film.
The passivation film (inorganic film) that passivator of the present invention enables aluminum alloy to surface formation by the multiple organic phosphoric acid polytype metal ion of associating can show a degree of color.
In chrome-free tanning agent of the present invention, HEDP is 1-hydroxy ethylidene-1,1-diphosphonic acid；HPMA is hydrolytic polymaleic anhydride；EDTMP is ethylene diamine tetra methylene phosphonic acid；DTPMP is that diethylenetriamine pentamethylene pitches phosphonic acids, ATMP is ATMP and PBTCA is phosphonobutane tricarboxylic acid.
Detailed description of the invention
According to following embodiment, it is possible to be more fully understood that the present invention.But, as it will be easily appreciated by one skilled in the art that the content described by embodiment is merely to illustrate the present invention, and should without the present invention described in detail in restriction claims.
Embodiment 1
A kind of chrome-free tanning agent suitable in aluminium alloy, is made up of following component: 200ppmN-methyl-γ-aminopropyltrimethoxysilane, 40ppm γ-glycydoxy methyldiethoxysilane, 40ppm nanoscale SiO2Particle, 10ppm nanoscale ZrO2Particle, 250ppm potassium fluorozirconate (in zirconium), 200ppm fluotitanic acid (in titanium), 100ppm cerous nitrate (in cerium), 40ppm cobalt nitrate (in cobalt), 100ppm sodium fluoride, 10ppm sodium citrate, 25ppmATMP, 50ppmHEDP, 30ppm nonionic surfactant and water surplus.
Embodiment 2
A kind of chrome-free tanning agent suitable in aluminium alloy, is made up of following component: 50ppm gamma-aminopropyl-triethoxy-silane, 100ppm γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, 30ppm nanosized TiO_2 particle, 20ppm nanoscale CeO2Particle, 50ppm nanoscale SiO2Particle, 120ppm45% fluorine zirconic acid (in zirconium), 60ppm potassium fluotitanate (in titanium), 10ppm copper nitrate (in copper), 50ppm cerous nitrate (in cerium), 60ppm cobalt nitrate (in cobalt), 150ppm potassium fluoride, 15ppm oxalic acid, 50ppmHEDP, 30ppmHPMA, 50ppm nonionic surfactant and water surplus.
Embodiment 3
A kind of chrome-free tanning agent suitable in aluminium alloy, is made up of following component: 240ppmN, N-diethyl-γ-aminopropyltrimethoxysilane, 60ppm2-(3,4-epoxycyclohexyl) ethyl triethoxysilane, 40ppm nanoscale SiO2Particle, 30ppm nanoscale TiO2Particle, 30ppm nanoscale CuO nanoparticle, 250ppm potassium fluorozirconate (in zirconium), 250ppm fluotitanic acid (in titanium), 90ppm cerous nitrate (in cerium), 60ppm cobalt nitrate (in cobalt), 150ppm sodium fluoride, 10ppm sodium citrate, 10ppm succinic acid, 50ppmEDTMP, 20ppmPBTCA, 30ppmHPMA, 30ppm nonionic surfactant and water surplus.
Comparative experimental example:
Model is processed by the chrome-free tanning agent prepared by embodiment 1:
Step 1, prepares model:
Adopting 6063 aluminium alloy test pieces, specification is the aluminium alloy model that (150mm × 70mm × 0.8mm) is used as implementing.
Step 2, defat pretreatment:
Washing degreaser according to quality than preparating acid: 0.5% sulphuric acid, 0.1% Fluohydric acid., 0.1% sodium citrate, 0.2%NP-10, surplus is water.The model of immersion treatment step 13 minutes at ambient temperature.
Step 3, the pretreated washing of defat processes:
Model after immersion treatment pickling ungrease treatment 1 minute in tap water clear water.
Step 4, adopts the chrome-free tanning agent that embodiment 1 prepares that model is processed:
Using aqueous sodium carbonate to regulate the chrome-free tanning agent that embodiment 1 obtains so that it is pH value is 3.25, the chrome-free tanning agent using pH value to be 3.25 processes model 3.0 minutes, and by observing, color occurs in specimen surface, and film forming develops the color simultaneously, it is easy to judge.
Step 5, the washing after chrome-free tanning agent process processes:
The model tap water processed through chrome-free tanning agent is cleaned 1 minute, re-uses deionized water rinsing 30 seconds.
Step 6, dries:
Model after chrome-free tanning agent processes and washes is put into 10min in 110 DEG C of baking ovens.
Step 7, powder coating:
Model after drying uses powdery paints (tiger metal dust) to carry out electrostatic spraying process, rear model after electrostatic spraying is solidified 20 minutes under 180 DEG C of conditions, taking out room temperature to place and detect its film thickness after 16h and namely obtain test piece in 50 μm ± 2 μ m, test piece specifically detects performance, and in Table 1, (wherein hundred lattice tests draw hundred lattice of 1mm × 1mm spacing to the adhesion after investigating powder coating for model after boiling water boiling 4h；Neutral salt spray test is used for investigating the corrosion resistance of passivation film).
Model is processed by the chrome-free tanning agent prepared by embodiment 2:
Step 1, prepares model:
Adopting 6063 aluminium alloy test pieces, specification is the aluminium alloy model that (150mm × 70mm × 0.8mm) is used as implementing.
Step 2, defat pretreatment:
Washing degreaser according to quality than preparating acid: 0.5% sulphuric acid, 0.1% Fluohydric acid., 0.1% sodium citrate, 0.2%NP-10, surplus is water.The model of immersion treatment step 13 minutes at ambient temperature.
Step 3, the pretreated washing of defat processes:
Model after immersion treatment pickling ungrease treatment 1 minute in tap water clear water.
Step 4, adopts the chrome-free tanning agent that embodiment 2 prepares that model is processed:
Using aqueous sodium carbonate to regulate the chrome-free tanning agent that embodiment 2 obtains so that it is pH value is 3.25, the chrome-free tanning agent using pH value to be 3.25 processes model 3.0 minutes, and by observing, color occurs in specimen surface, and film forming develops the color simultaneously, it is easy to judge.
Step 5, the washing after chrome-free tanning agent process processes:
The model tap water processed through chrome-free tanning agent is cleaned 1 minute, re-uses deionized water rinsing 30 seconds.
Step 6, dries:
Model after chrome-free tanning agent processes and washes is put into 10min in 110 DEG C of baking ovens.
Step 7, powder coating:
Model after drying uses powdery paints (tiger metal dust) to carry out electrostatic spraying process, rear model after electrostatic spraying is solidified 20 minutes under 180 DEG C of conditions, taking out room temperature to place and detect its film thickness after 16h and namely obtain test piece in 50 μm ± 2 μ m, test piece specifically detects performance, and in Table 1, (wherein hundred lattice tests draw hundred lattice of 1mm × 1mm spacing to the adhesion after investigating powder coating for model after boiling water boiling 4h；Neutral salt spray test is used for investigating the corrosion resistance of passivation film).
Model is processed by the chrome-free tanning agent prepared by embodiment 3:
Step 1, prepares model:
Adopting 6063 aluminium alloy test pieces, specification is the aluminium alloy model that (150mm × 70mm × 0.8mm) is used as implementing.
Step 2, defat pretreatment:
Washing degreaser according to quality than preparating acid: 0.5% sulphuric acid, 0.1% Fluohydric acid., 0.1% sodium citrate, 0.2%NP-10, surplus is water.The model of immersion treatment step 13 minutes at ambient temperature.
Step 3, the pretreated washing of defat processes:
Model after immersion treatment pickling ungrease treatment 1 minute in tap water clear water.
Step 4, adopts the chrome-free tanning agent that embodiment 3 prepares that model is processed:
Using aqueous sodium carbonate to regulate the chrome-free tanning agent that embodiment 3 obtains so that it is pH value is 3.25, the chrome-free tanning agent using pH value to be 3.25 processes model 3.0 minutes, and by observing, color occurs in specimen surface, and film forming develops the color simultaneously, it is easy to judge.
Step 5, the washing after chrome-free tanning agent process processes:
The model tap water processed through chrome-free tanning agent is cleaned 1 minute, re-uses deionized water rinsing 30 seconds.
Step 6, dries:
Model after chrome-free tanning agent processes and washes is put into 10min in 110 DEG C of baking ovens.
Step 7, powder coating:
Model after drying uses powdery paints (tiger metal dust) to carry out electrostatic spraying process, rear model after electrostatic spraying is solidified 20 minutes under 180 DEG C of conditions, taking out room temperature to place and detect its film thickness after 16h and namely obtain test piece in 50 μm ± 2 μ m, test piece specifically detects performance, and in Table 1, (wherein hundred lattice tests draw hundred lattice of 1mm × 1mm spacing to the adhesion after investigating powder coating for model after boiling water boiling 4h；Neutral salt spray test is used for investigating the corrosion resistance of passivation film).
Comparative example 1: with certain commercially available Cr VI passivator, model is processed:
Step 1, prepares model:
Adopting 6063 aluminium alloy test pieces, specification is the aluminium alloy model that (150mm × 70mm × 0.8mm) is used as implementing.
Step 2, defat pretreatment:
Washing degreaser according to quality than preparating acid: 0.5% sulphuric acid, 0.1% Fluohydric acid., 0.1% sodium citrate, 0.2%NP-10, surplus is water.The model of immersion treatment step 13 minutes at ambient temperature.
Step 3, the pretreated washing of defat processes:
Model after immersion treatment pickling ungrease treatment 1 minute in tap water clear water.
Step 4, adopts certain commercially available Cr VI passivator that model is processed:
Using aqueous sodium carbonate to regulate Cr VI passivator so that it is pH value is 3.25, the Cr VI passivator using pH value to be 3.25 processes model 3.0 minutes, and by observing, color occurs in specimen surface.
Step 5, the washing after the process of Cr VI passivator processes:
The model tap water processed through Cr VI passivator is cleaned 1 minute, re-uses deionized water rinsing 30 seconds.
Step 6, dries:
Model after Cr VI passivator processes and washes is put into 10min in 110 DEG C of baking ovens.
Step 7, powder coating:
Model after drying uses powdery paints (tiger metal dust) to carry out electrostatic spraying process, rear model after electrostatic spraying is solidified 20 minutes under 180 DEG C of conditions, taking out room temperature to place and detect its film thickness after 16h and namely obtain test piece in 50 μm ± 1 μ m, test piece specifically detects performance, and in Table 1, (wherein hundred lattice tests draw hundred lattice of 1mm × 1mm spacing to the adhesion after investigating powder coating for model after boiling water boiling 4h；Neutral salt spray test is used for investigating the corrosion resistance of passivation film).
Table 1
Passivator of the present invention adopts at zirconium, titanium system adds many kinds of metal ions and multiple nanoparticle, different types of metal ion, nanoparticle and the collaborative film forming of silane coupler, farthest avoid the infiltration of corrosive medium, reduce the generation of base material corrosion, in addition combined with organic phospho acid multiple in component, not only be effectively increased passivation film corrosion resistance and with the physical bond ability of post-coatings, reach the thicknesses of layers of Cr VI passivator, the rete of certain color can also be formed in aluminum alloy surface simultaneously, Field Force is facilitated to pass through color quick, judge whether passivation film is formed easily.
Claims (10)
1. the chrome-free tanning agent being applicable to aluminium alloy, it is characterized in that: for every L chrome-free tanning agent, be made up of the component of following quality: the amino silane of 10～300mg or/and epoxy silane, the dispersibility nanoparticle of 1～100mg, 10～500mg zirconium compounds or/and titanium compound, the metal ion of 1～150mg, the fluoride of 10～150mg, 1～20mg chelating agent, the organic phosphoric acid of 75～100mg and surplus are water；Wherein, described organic phosphoric acid is at least two in HEDP, HPMA, EDTMP, DTPMP, ATMP and PBTCA.
null2. the chrome-free tanning agent suitable in aluminium alloy according to claim 1，It is characterized in that: described amino silane is γ-aminopropyltrimethoxysilane、Gamma-aminopropyl-triethoxy-silane、γ-aminopropyltriethoxy dimethoxysilane、γ-aminopropyltriethoxy diethoxy silane、N-methyl-γ-aminopropyltrimethoxysilane、N-(normal-butyl)-γ-aminopropyltrimethoxysilane、N-(normal-butyl)-gamma-aminopropyl-triethoxy-silane、N，N-diethyl-γ-aminopropyltrimethoxysilane、3-cyclohexyl-aminopropyltriethoxy dimethoxysilane、Anilinomethyl trimethoxy silane、Anilinomethyl triethoxysilane、N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane、N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane、N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane、N-(β-aminoethyl)-γ-aminopropyltriethoxy diethoxy silane、Aminoethyl ammonia isobutyl methyl dimethoxysilane、3-(2-ethoxy aminoethyl)-aminopropyltriethoxy dimethoxysilane、Diethylenetriamine base hydroxypropyl methyl dimethoxysilane、One in double; two [3-(trimethoxy-silylpropyl)] amine or double; two [3-(triethoxysilylpropyltetrasulfide)] amine.
3. the chrome-free tanning agent suitable in aluminium alloy according to claim 1, it is characterized in that: described epoxy silane is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-(2,3-epoxy the third oxygen) hydroxypropyl methyl dimethoxysilane, γ-glycydoxy triethoxysilane, γ-glycydoxy methyldiethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, one in 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane.
4. the chrome-free tanning agent suitable in aluminium alloy according to claim 1, it is characterised in that: described dispersibility nanoparticle is SiO2Nanoparticle, ZrO2Nanoparticle, HfO2Nanoparticle, LaO2Nanoparticle, CeO2Nanoparticle, TiO2Particle, Al2O3Nanoparticle, MnO2Nanoparticle, MoO3Nanoparticle, CuO nanoparticle, B2O3Nanoparticle or Co2O3Any two or three nanoparticle in nanoparticle.
5. the chrome-free tanning agent suitable in aluminium alloy according to claim 1, it is characterised in that: described zirconium compounds is the one in fluorine zirconic acid, zirconium oxychloride, zirconium carbonate, zirconium nitrate or zirconyl nitrate.
6. the chrome-free tanning agent suitable in aluminium alloy according to claim 1, it is characterised in that: described titanium compound is fluotitanic acid or titanyl sulfate.
7. the chrome-free tanning agent suitable in aluminium alloy according to claim 1, it is characterised in that: described metal ion is the metal ion in rare earth element or at least two in Fe, Mg, Co, Cu, Zn or Mo.
8. the chrome-free tanning agent suitable in aluminium alloy according to claim 1, it is characterised in that: described fluoride is sodium fluoride or potassium fluoride.
9. the chrome-free tanning agent suitable in aluminium alloy according to claim 1, it is characterised in that: described chelating agent is at least one in sodium citrate, sodium tartrate, oxalic acid, malic acid, succinic acid or malonic acid.
10. the chrome-free tanning agent suitable in aluminium alloy according to claim 1, it is characterized in that: in every L chrome-free tanning agent, possibly together with a certain amount of surfactant, described surfactant is the one in cationic surface active agent, anionic surfactant, amphoteric surfactant or nonionic surfactant.
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| WO2019006611A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市宏昌发科技有限公司 | Passivator, method of surface passivation of metal-plated part and metal workpiece |
| CN107475704A (en) * | 2017-07-11 | 2017-12-15 | 沈阳瑞驰表面技术有限公司 | Metal surface silane treatment agent and preparation method thereof |
| CN107236946A (en) * | 2017-08-13 | 2017-10-10 | 上海釜强智能科技有限公司 | A kind of colored chromium-free passivation liquid |
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| TWI640653B (en) * | 2018-01-18 | 2018-11-11 | 國立高雄大學 | Anti-corrosion solution having nano titanium dioxide particles chelated with aniline and manufacturing method thereof |
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| CN109440121A (en) * | 2018-12-25 | 2019-03-08 | 成都四吉达新材料科技有限公司 | A kind of processing technology of aluminum veneer |
| CN109943834A (en) * | 2019-03-28 | 2019-06-28 | 江苏鑫露化工新材料有限公司 | It is a kind of for enhancing zirconium, the additive of titanium compound inactivating performance and its application |
| CN109913926A (en) * | 2019-04-17 | 2019-06-21 | 安徽华淮新材料有限公司 | Aluminium alloy anode oxide film hole sealing agent and its method for sealing |
| CN111893468A (en) * | 2020-07-05 | 2020-11-06 | 江苏荣企新材料科技有限公司 | Aluminum-magnesium alloy metal frame surface corrosion-resistant treatment process |
| CN112301340A (en) * | 2020-09-29 | 2021-02-02 | 九牧厨卫股份有限公司 | Stainless steel passivation solution and method for improving corrosion resistance of stainless steel wire drawing floor drain |
| CN113621956A (en) * | 2021-07-15 | 2021-11-09 | 深圳市豪龙新材料技术有限公司 | Chromium-free die-casting aluminum sealant, preparation method and application thereof |
| CN113699514A (en) * | 2021-07-29 | 2021-11-26 | 马鞍山钢铁股份有限公司 | Zinc-aluminum-magnesium coating passivator, passivation film and passivation plate |
| CN113699514B (en) * | 2021-07-29 | 2022-12-27 | 马鞍山钢铁股份有限公司 | Zinc-aluminum-magnesium coating passivator, passivation film and passivation plate |
| CN113862652A (en) * | 2021-09-06 | 2021-12-31 | 广东致卓环保科技有限公司 | Chromium-free passivation solution for pretreatment of die-casting aluminum alloy for vehicle and use process thereof |
| CN115216760A (en) * | 2022-06-23 | 2022-10-21 | 安徽舜邦精细化工有限公司 | Slag-free coating agent |
| CN115216760B (en) * | 2022-06-23 | 2024-01-16 | 安徽舜邦精细化工有限公司 | Slag-free coating agent |
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